Gas purification



April 5, 1932.

C. J. HANSEN GAS PURIFICATION Original Filed Aug. 20, 1928 Patented Apr. 5, v1932 UNITED STATES PATENT OFFICE CHRISTAN J. HANSEN, GF ESSEN-EUHR, GERMANY, ASSG-NOR, BY MESNE ASSIGN- MENTS, TO THE KOPPERS COMPANY, PORATION OF DELAWARE F PITTSBURGH, PENNSYLVANIA, Ay COR- ens PURIFICATION Original application filed August 20, 1923, Serial No. 300,945, and in Germany ctober 22, 1927.` Divided and this application led December 4, 1929. SeriaI No. 411,687.

My invention refers to the treatment of gases, more especially gases such as result 1n the distillation of coal and other carbonaceous material and is diagrammatically illustrated by the accompanying flow sheet. It is a particular object of my invention to provide means whereby the ammonia and sulfur which are contained in such gases, the latter mostly under the form of hydrogen sulfide, can be recovered from the gases in an easier and more perfect manner than was hitherto possible.

It is known to recover the ammonia and hydrogen sulfide from gases by means of solutions of metal thionates. In this process there results metal sulfide and a solution of ammonium thionate and in some cases also free sulfur.

The meta-l sulfide, which may be ferrie sulfide, manganese sulfide `or zinc sulfide is re` dissolved by acting thereon with sulfur dioxide and there results a. metal thionate solution and free sulfur. This solution has hitherto been treated further in such manner that the solution containing, besides sulfur, metal and ammonium thionates in solution was decom- V posed by heating into sulfate and sulfur, and

l other acids.

The metal thionate solutions described are further able only to take up ammonia and hydrogen suliidein the predetermined pro- E portion of 2NH3: lHgS. Now in view of the `fact that the gases resulting for instance in the distillation of coal always contain more hydrogen sulfide (gasresultinginthe distillation of Ruhr coal about 50 per cent, English coal partly 100 to 200 per cent more than corresponds to the above proportion), a process of purification as above described always leaves a more or less considerable proportion of hydrogen sulfide in the gas.

It is further known to remove hydrogen sulfide from gases free from ammonia by ferent means such as l. Solutions of polythionates, y

2. Solutions of thiosulfates, to which sulfur dioxide is added, n

3. Suspensions of ferrie hydroxide.

The means recited above for recovering the hydrogen sulfide differ as regards their velocity of reaction'.

The slowest acting is thesolution of polythionates while a thiosulfate solution, to which sulfur dioxide is added, will act somewhat more quickly. However the velocity of reaction of these solutions is always so small that in the case of polythionate solution and a gas containing for instance 0,8 per cent H2S,only 33 per cent of the hydrogen sulfidecan be removed, with a solution of thiosulfate and sulfur dioxide only about 50 per cent per unit of time. y

@n theother hand a suspension .of ferrie hydroxidewill act on a gas washing liquor having neutral or vslightly alkaline reaction so favorably `that the total removal of hydrogen sulfide can be effected und-er commercial conditions.

Unfortunately the use of suspensions of ferric hydroxide involves the great disadvantage, that when the spent washing liquor is regenerated with air or another gas containing oxygen, there resul-ts a mixture of ferric hydroxide and sulfur and the separation Y ofthe sulfur from the iron sludge is very ex# pensive. One is further forcedrto keep thev percentage of iron in such solutions as low as possible in order to obtain the most favorable proportionbetween the sulfur and the iron. This entails the drawback, that the absorbing capacity of such washing liquorfor hydrogen sulfide is comparatively small.

With an iron content of about 2 kgs. per cubicmeter of the solution, not more than 100 cubicmeter gas can be treated at the utmost. In my copending application for patent of the United States Serial Number 300,945, I have described a method of treating coke oven gases for the recovery therefrom of useful admixtures, which allows obviating the drawbacks inherent in both absorption modes by carrying them out inVV succession. It consulfide and ammonia are absorbed.

This method allows removing, besides' the` ammonia contents, .all the hydrogen-sulfidel from a gas irrespective of the ratio of the contents of these two admiXtures and more particularly from a gas which contains evenH less than 2l\lI-I3 per lHgS. On the other hand the elementary' sulfur obtained can readily be recovered in a pure state free of ferrie or manganese hydroxide by mixing the two different Washing liquors when spent, dividing the mixtures into two parts and separately regenerating each part by treating it with air or sulfur dioxide, respectively. While the suspensionrof free sulfur and ferrie or manganese hydroxide obtained by blowing with air is immediately reused, the liquor obtained by the introduction ofsulfurfdioxide, which. contains iron. or manganese thionates in solution and elementary sulfur in suspension, is first filtered, whereby the sulfur is obtainedrinrapure state tree offerric or manganesehydroxide; Y s This `method which requires the use of ferrie or manganesehydroxide can be modilied in accordance :with my invention by replacing-the aqueous suspension of ferrie lor manganesehydroxide by asolution of a poly? thionate, preferably of an ammonium polythionate, whichgis obtained .by introducing sulfur dioXideinto a solution yof ammonium thiosulfate, .and allowing .the reaction mix'- ture. to stand fora sufficient .period of time, preferably at a slightly elevated temperature. It also displays an absorptive power on :hydrogen sulfide even in thefabsence-of freeanr moni'a, ammonium. thiosulfate and. free sulfur being-formed.v While thisV solution is not so strongly absorptive'as to remove the lastltracesfof-hydrogen.sulfide froma gas within .a convenientperiod of contact time,

Y it-mayadvantageouslybe used for removing that part of hydrogen suliide from the crude gas, which exceed-s the proportion of In my vcopendingapplication for patent ofrvthe'United States Serial No. 411,688, filed Vofeven date, I'have described a method of treating Acoal distillation gasesV which comprises'the step of Apreliminary washing the gas with a solution containing a Complex compound of th-iosulfate and sulfur dioXide. Such complex compound being distinguished from polythionates by its ycomparatively deeper yellow color and by its more intense absorption power on hydrogen sulfide, I wish it tobe understood that the expressionfpoly thionate used in the present specification and' in the Vclaims a'xed thereto is intended to mean a solution of a polythionate free of such complex compound ofthiosulfate and sulfur dioxide.

It will be understood that by the combined use of'twowashing liquors, one of'which contains ammonium polythionate7 while the other one Contains thionates of the'iron group in solution, l may also completely remove all the ammo-nia and hydrogen vsulfide contents from the gas irrespective of their proportion, i.v e'even in such cases where an excess of hydrogen sulfide over the proportion 2NH3 lHgS is present. However, since the absorption of'hydrogen sulfide by the metal thionate solution is only-possible in the presence of an at least equivalent amount of ammonia, care should be taken to avoid an undue absorption of ammonia by the washing liquor containing the ammonium polythionate. For this reason I do not employ, in the practice of my invention the so-called directway of separatingrammonia, i. e. the treatment' with the washing liquors of a gas which contains substantially all the original am'- monia, but I prefer separating at least part of the ammoniafrom such gas prior to the washing with the solution of the ammonium polythionate. The ammonia thus-separated is used in vthe other-washing step for adjusting therein the proportion of ammonia and hydrogen sulfide, so as to bring about a complete absorptionoi' both substancesin this latter washingstage.

Vhether substantially all the ammonia contained in the crude gas,'or only part of it, should be separated out prior to the first washing step, depends on the additional amount of ammonia required in the second washing step. l

If it is desired to use a semi-direct method in which the gas is lirst cooled down vigorously, so thatpart of the ammonia is dissolved in.Y gas liquor to be recovered therefrom by distillation, preliminary washing of the gases in order to remove part of thehydrogen sulfide may be effected by means of a solution containing ammonium polythionate only in such cases where a comparatively high content of ammonia is lpresent in the gas, or a comparatively great proportion of the 'hydron gen suliide is absorbed in the firstwashing y lt is however also possibleto con-V ammonia liquor, vwhen distilling same, from hydrogen sulfide and carbon dioxide.

If it is desired to use an indirect process, i. e. a'process in which the gas is first cooled down, part of the ammonia contained there- 1n being recovered m the form of gas liquor,

i method.

The particular technical advantage of these ,modes of operating consists therein, that they can easily be adapted to widely differing conditions of operation and to all kinds of apparatus. v

The purification effect is practically independent from all variations in the composition of the gas and in the production, more especially when different kinds of gas are produced. The possibility of accumulating either allor the greater part of the ammonia contained in the gas, renders it possible, for instance for the purpose of repairs, to temporarily throw out'one or the other regeneration apparatus, so that the operation of the process is thus rendered uniform in an extraordinary degree.

In order to carry out the purification proper, a solution of ammonium thiosulfate whichvmay for instance contain 10-60 per cent thiosulfate, is treated with sulfur dioxide in a separate apparatus so as to obtain an intensively yellow liquor, which is then introduced into the preliminary washer. However the required quantity of sulfur dioxide can also be added to the gas before it enters the preliminary washer. During the absorption free sulfur is formed from the hydrogen sulfide extracted from the gas and from a corresponding quantity of sulfur dioxide. It does not mattenwhether solutions containing metal or free .from metal are used. 4If the washing lioluor is spent, I may regenerate-it, or part of it, by introducing sulfur dioxide. The regenerated liquor is reused in cycle, but part of it may be withdrawn and heated for the recovery therefrom of ammonium sulfate and sulfur.

The concentrated ammonia obtained by distillation of the watery liquors containing ammonia is conducted without previous purification into the second washing stage operating with metal thionates This solution, ifspent, may also be regenerated by means of sulfur dioxide, and reused in cycle.

In order to recover from the concentrated A solution of ammoniumsalt the sulfate .and

sulfur it is preferable, in contradistinction to the methods hitherto employed, according to which the ammonium sulfate solution was ultimately obtained freed from metal by acting thereon with fresh gas, to insert this step in the process, before the sulfate is formed, as only by so doing the formation of ferrie disuliides (FeS2) can be prevented, which cannot be dissolved by treatment with sulfur dioxide.

While the ferrie or manganese sulfide thus formed is filtered off, and supplied to the regenerator, the filtrate, i. e. the solution` of ammonia thionates may be treated with sulfur dioxide, and heated, in order to form ammonium sulfate and sulfur; but I may also admix this solution to the washing liquorof the `other washing cycle. A

My invention at the same time enables me f to extract from the gas also the cyanogen contained therein and to convert same into ammonium thiocyanate, from which can then be obtained ammonium sulfate and sulfur in the lmanner described in my copending application for Letters Patent of the United States for improvements in treating thiocyanates, Serial No. 298,617.

In this copending application I have shown that if ammonium thiocyanate is'decomposed hydrolytically within the washing liquor, which results in the purification of coal distillation gases, such washing liquor containing either polythionates or corresponding quantities of thiosulfate and sulfur dioxide combined loosely withl each other, or, if such salts 0r sulfur dioxide or both are introduced into the liquor, orv if ammonium bisulfite or ammonium sulite are present therein, ammonium sulfate and free sulfur will result. I have further shown that these conversions of ammonium thiocyanate takeplace slowly at ordinary temperature and more rapidly at an 'elevated temperature, more especially under pressure, preferably at a temperature `varying between Mtl-160 C.

As al1 the washing liquors usedin the purification of the gas contain free sulfur and as the solution of ammonium polythionate as well as the iron thionate solutions can` co,ntain some ammonia during the washingpro* cedure, they will also absorb from the gas all cyanogen compounds, which are converted into ammonium thiocyanate. Vhen treating the spent washing liquors forthe production of ammonium sulfate and sulfur, the ammonium thiocyanate is also converted into ammonium sulfate and free sulfur.

p Thus the yield of ammonium sulfate in a gas washing process is materially increased for the first time.

It is well known that the` cyanogen compounds in the gas are formed incandescent coal and the hot products of ':distillation,fis lconverted into 4cyanogenicoms pounds. l@Thereby hithertoia material propor- .tion of the ammonia,.iabout;10-20per cent .and more was decomposed. WThe present griprocess thereforeaenables ine to obtain"10.-;2O

.per .cent and more ammoiiium-V sulfate iii excess of` the quantity: .hitherto obtainable.

Ema/imple] @lo A coke oven gas which contains ata temform of FeS from the spentiwashing liquor oflthe Vsecond washing stage is supplied to Vthe first washing cycle. 'Part'of-theregenerated liquor ofthis first cycle, from which A free-sulfur maybe filtered off, andwhich *z5 thereafter containsl besides ammonium polythio-nate also ammonium "t'hiocyanate,y is heated as described-inmy copending application for patent Vmentioned labove, the thiovcyanateis,converted in thesan'ieinanner as l' So 'theiainmoniuin polytliionate into vammonium sulfate and sulfur. I thusobtai-ii an increase inv the ryield of ammonium sulfate formed from the ammonia inv the-gas,fwhichvainounts -tolt per cent, the nitrogen contents ofthe i V'35 Ikcyaiiogen compounds being also converted into ammonia.

. -Eample Afsalt solution isL treated as described-'with Y. o reference to kExample l, how-ever the liquor is-not heated at once,but isallo-wed to stand some time-'after the sulfur dioxide haslbeen introduced. The'thiosulfa-te in solution will then begradually converted `undertheaction of the sulfur dioxide into polythionates, in the first line'trior tetrathionate. If the solution is then heated, which now; mainly'contains,'instea'd of the'thiosulfate and sulfur dioxide, polythionates and ammoniumrthio- "'39 cyanate, the heating being effected as described with reference to Example 1,exactly thesame'result will'be obtained including the same quantities of ammonium'sulfate,

55 sulfur land carbon dioxideasinExample l.

, .Obviously the proportions given in the examples7 needV not be the same throughout,

but .all such-solutions can be treated for'the recovery of sulfateand sulfur which contain,

.-59 besides iammonium thiocyanate,ammonium hiosiilfate, sulfur dioxide, ammonium poly- Qthionateand sulfuric'acid. Sulfitesf and bi- .sulfites may also be present.

:In calculating the f composition Aof 65,'solutionsi the following irules apply such 11. `1:]5IH'4GNS? isdecomposed .'to formf sulfate and'sul'fur `by means of n.12 moleculesrSO2 119.12 molecules polythionate ,0.12 fmolecules fthiosulfate+ '3 "molecules cl. `8molecules bisulfite V@.12 -v-molecules thiosulfate-l-.2 tmolecules HgSO4.

2. .Thfiosulfates, sulites,'bisultes and polythionates vare decomposed under `the"'forma f'tionof sulfate andV sulfur `according tol` the ifllowing Yrules "m12 'molecules fithiosulfate l 'molecule Y polythionate y 6.12 molecules lsu'lite-l-'l `molecule `polyythionate c. 2 molecules bisulfite-tl molecule'thiosulfate Y d. 2 .molecules bisulite+l molecule sulg,

vite. i f

Any of these: stocks mayfbelmixed'fwith each other in any desired proportion-andfin yall cases sulfate and sulfur will'result.v IfV more suliitel or thiosulfate is present than.; Vcorresponds to these prescriptions, fnon-decomposed'thiosulfate and, ifammonium' thiocyanate 'is present, also non-decomposed 1ammonium thiocyanate will remain in solution.

'On the other hand if the-solution contains more bisuliite or more polythionate thanY indicated above, there are-formed' besides sul- IfateA and sulfur moreor less free' sulfuric-acid yand,-if ammonium thiocyanate is present, also carbon dioxide. In-su'ch'case,'as shown above, the mother liquor rich in sulfuric acid which i remains overV whenfevaporating v for the recovery of sulfate, is preferably returned into the decomposition vessel.

Various changesmay bemade in the details disclosed in the foregoing'specification without'departing from the invention 'or sacrificing the advantages thereof.

I claim i. YThe method @firming mi' distillation gases for the recovery therefrom of vuseful admixtures which comprises separating ammonia from such gas, thereafter washing said gas with a solution'containing ammonium polythionate to remove partof thehydrogen .fl

sulfide contained in said gas, thereafter Ywashing said gas with asolution of a thioiiate of the iron group in order to remove'resi'dual hydrogen sulfide 'from'sai/d gas and adding to the washingV liquor containing a'ftl'iionatel of the iron group at least part of'tlievamvmonia previously separated. f Y 1 2. 'The method of treating coal distillati-on gases for the recovery therefrom-of useful admixtures which comprises cooling'the 'gas'tj below its dew point'in order tocondense a gas liquor containing part of the ammonia Y contained in said gas, washing the gasithus treated ata temperature. below itsdew'point with :water V'to remove 4residual ammonia,

thereafter Washing said gas With a solution containing ammonium polythionate to remove part of the hydrogen sulde contained in said gas, thereafter Washing said gas With a solution of a thionate of the iron group in order t0 remove residual hydrogen sulde from said gas, and adding to the Washing liquor containing a thionate of the iron group at least part of the ammonia previously separated.

In testimony whereof I aiix my signature.

CHRISTIAN J. HANSEN. 

